Substrate treating apparatus

ABSTRACT

A substrate treating apparatus and a method of treating a substrate, the apparatus including a substrate treater that treats a substrate using a chemical solution, the chemical solution including a phosphoric acid aqueous solution and a silicon compound; and a chemical solution supplier that supplies the chemical solution to the substrate treating unit, wherein the chemical solution supplier includes a concentration measurer that measures concentrations of the chemical solutions, the concentration measurer including a first concentration measurer that measures a water concentration of the chemical solution; and a second concentration measurer that measures a silicon concentration of the chemical solution.

CROSS-REFERENCE TO RELATED APPLICATIONS

This is a divisional application based on pending application Ser. No.15/175,062, filed Jun. 7, 2016, the entire contents of which is herebyincorporated by reference.

Korean Patent Application No. 10-2015-0124255, filed on Sep. 2, 2015, inthe Korean Intellectual Property Office, and entitled: “SubstrateTreating Apparatus and Method of Treating Substrate,” is incorporated byreference herein in its entirety.

BACKGROUND

1. Field

Embodiments relate to a substrate treating apparatus and a method oftreating a substrate.

2. Description of the Related Art

As semiconductor memory devices are highly integrated, reliability andelectrical characteristics of semiconductor memory devices may begreatly affected by damage and variation of components constituting thesemiconductor memory devices.

SUMMARY

Embodiments are directed to a substrate treating apparatus and a methodof treating a substrate.

The embodiments may be realized by providing a substrate treatingapparatus including a substrate treater that treats a substrate using achemical solution, the chemical solution including a phosphoric acidaqueous solution and a silicon compound; and a chemical solutionsupplier that supplies the chemical solution to the substrate treatingunit, wherein the chemical solution supplier includes a concentrationmeasurer that measures concentrations of the chemical solutions, theconcentration measurer including a first concentration measurer thatmeasures a water concentration of the chemical solution; and a secondconcentration measurer that measures a silicon concentration of thechemical solution.

The embodiments may be realized by providing a method of treating asubstrate, the method including supplying a chemical solution to asubstrate to perform a process on the substrate, the chemical solutionincluding a silicon compound and a phosphoric acid aqueous solution;circulating the chemical solution; sampling at least a portion of thecirculated chemical solution; measuring a water concentration and asilicon concentration of the sampled chemical solution; and processingconcentration data of the chemical solution based on the waterconcentration and the silicon concentration.

The embodiments may be realized by providing a method of treating asubstrate, the method including supplying a chemical solution to asubstrate to perform a process on the substrate, the chemical solutionincluding a silicon compound and a phosphoric acid aqueous solution;circulating the chemical solution; sampling at least a portion of thecirculated chemical solution; and measuring a water concentration and asilicon concentration of the sampled chemical solution, whereinmeasuring the silicon concentration includes preventing a measurementerror of the silicon concentration and preventing a silicon deposit,which occur by the silicon concentration increasing during the process.

The embodiments may be realized by providing a method of treating asubstrate, the method including supplying a chemical solution to asubstrate to perform a process on the substrate, the chemical solutionincluding a silicon compound and a phosphoric acid aqueous solution;circulating the chemical solution; sampling at least a portion of thecirculated chemical solution; and measuring a water concentration and asilicon concentration of the sampled chemical solution, whereinperforming the process on the substrate increases the siliconconcentration of the chemical solution, and measuring the siliconconcentration includes cleaning a silicon concentration measurer thatmeasures the silicon concentration.

BRIEF DESCRIPTION OF THE DRAWINGS

Features will be apparent to those of skill in the art by describing indetail exemplary embodiments with reference to the attached drawings inwhich:

FIG. 1 illustrates a schematic block diagram of a substrate treatingapparatus according to some embodiments.

FIG. 2 illustrates an enlarged view of a second concentration measuringpart of FIG. 1.

FIG. 3 illustrates an enlarged view of a waste solution treating part ofFIG. 1.

FIG. 4 illustrates a flow chart of a method of treating a substrateaccording to some embodiments.

FIG. 5A illustrates a flow chart of a process of measuring a waterconcentration and a silicon concentration of FIG. 4.

FIG. 5B illustrates a flow chart of a process of exhausting a wastesolution of FIG. 4.

FIG. 5C illustrates a flow chart of a process of processing data of FIG.4.

FIGS. 6A to 6E illustrate views of stages in the method of treating asubstrate of FIG. 4.

FIGS. 7A and 7B illustrate graphs according to a process of processingdata.

FIG. 8 illustrates a flow chart of a method of treating a substrateaccording to some embodiments.

FIG. 9A illustrates a flow chart of a process of cleaning a siliconconcentration measuring part of FIG. 8.

FIG. 9B illustrates a graph of a trend of a measured siliconconcentration.

DETAILED DESCRIPTION

FIG. 1 illustrates a schematic block diagram of a substrate treatingapparatus 1 according to some embodiments. FIG. 2 illustrates anenlarged view of a second concentration measuring part or secondconcentration measurer 264 of FIG. 1. FIG. 3 illustrates an enlargedview of a waste solution treating part or waste solution treater 280 ofFIG. 1. The substrate treating apparatus 1 will be described withreference to FIGS. 1 to 3 hereinafter. The substrate treating apparatus1 may include a substrate treating unit or a substrate treater 10, achemical solution supply unit or chemical solution supplier 20, and acontrol unit or controller 30.

The substrate treating unit 10 may include a bath 12. The bath 12 mayinclude a main bath 12 a and an assistant or auxiliary bath 12 b. Aprocess of treating a substrate may be performed using a chemicalsolution in the main bath 12 a. In some embodiments, an etching processmay be performed on a substrate in the main bath 12 a. In someembodiments, at least one of various processes of treating a substrateusing a chemical solution may be performed in the main bath 12 a. Achemical solution may be provided into the main bath 12 a, and asubstrate may be immersed in the chemical solution so as to be treated.The chemical solution may include a phosphoric acid aqueous solution anda silicon compound. The chemical solution may include ahigh-concentration silicon compound. For example, the chemical solutionmay include the silicon compound in a concentration of about 80 ppm toabout 1,000 ppm. The chemical solution may be controlled or maintainedat a high temperature to treat the substrate. For example, thetemperature of the chemical solution may be controlled to be maintainedat about 150° C. to about 200° C. For example, the process of using thechemical solution may be performed at a temperature of about 150° C. toabout 200° C.

A treating process may be performed on a plurality of substrates at thesame time in the main bath 12 a. The assistant bath 12 b may receive achemical solution overflowing from the main bath 12 a. The bath 12 maybe formed of a material with excellent thermal stability. In animplementation, a coating layer may be provided on inner surfaces of thebath 12.

The chemical solution supply unit 20 may include a chemical solutioncirculating part or chemical solution circulator 220, a sampling line240, a concentration measuring part or concentration measurer 260, and awaste solution treating part or waste solution treater 280. The chemicalsolution circulating part 220 may circulate a chemical solution providedinto the substrate treating unit 10. For example, the chemical solutioncirculating part 220 may circulate a chemical solution exhausted fromthe main bath 12 a and may then re-provide the circulated chemicalsolution to the assistant bath 12 b. The chemical solution may becontrolled to have a suitable process condition while the chemicalsolution is circulated in the chemical solution circulating part 220.For example, a temperature and/or a concentration of the chemicalsolution may be controlled or adjusted while the chemical solution iscirculated in the chemical solution circulating part 220. The chemicalsolution circulating part 220 may include a circulating line 222, acirculating heater 224, and a pump 226. One end of the circulating line222 may be connected to the bath 12, and another end of the circulatingline 222 may also be connected to the bath 12. The circulating heater224 and the pump 226 may be provided on the circulating line 222. Thecirculating heater 224 may heat a chemical solution in the circulatingline 222. The pump 226 may adjust a flow rate of a chemical solutionre-provided into the substrate treating unit 10. In an implementation, afilter may be installed on the circulating line 222.

The sampling line 240 may be connected to the chemical solutioncirculating part 220 and the concentration measuring part 260. At leasta portion of the chemical solution circulated in the chemical solutioncirculating part 220 may be sampled through the sampling line 240 so asto be provided into the concentration measuring part 260. An on-offvalve 242 may be provided on the sampling line 240. A first samplingline 240 a and a second sampling line 240 b may branch off from thesampling line 240. The first sampling line 240 a and the second samplingline 240 b may be respectively connected to a first concentrationmeasuring part 262 and a second concentration measuring part 264 whichwill be described below. A first sampling valve 242 a and a secondsampling valve 242 b may be provided on the first sampling line 240 aand the second sampling line 240 b, respectively. An addition line 244(connected to the assistant bath 12 b) may be connected to the samplingline 240 between the on-off valve 242 and the sampling valves 242 a and242 b. By operating an additional valve 244 a on the additional line244, a flow rate of a chemical solution may be adjusted and/or thechemical solution may be provided into the assistant bath 12 b.

The concentration measuring part 260 may include a first concentrationmeasuring part or first concentration measurer 262 and a secondconcentration measuring part or second concentration measurer 264. Thefirst concentration measuring part 262 and the second concentrationmeasuring part 264 may be connected in parallel to each other. Theconcentration measuring part 260 may sample a chemical solution tomeasure a concentration of the chemical solution. The firstconcentration measuring part 262 may measure a water concentration ofthe chemical solution. The first concentration measuring part 262 mayinclude an optical measuring part. For example, the first concentrationmeasuring part 262 may include an optical measuring part or opticalmeasurer using near-infrared rays. For example, the first concentrationmeasuring part 262 may irradiate the near-infrared rays to the chemicalsolution and may measure an absorption degree (i.e., an absorbance) froma wavelength band of a near-infrared ray, absorbed by water, amongnear-infrared rays reflected from the chemical solution. The firstconcentration measuring part 262 may convert the measured absorbanceinto a water content to measure the water concentration.

Referring to FIGS. 1 and 2, the second concentration measuring part 264may measure a silicon concentration of the chemical solution. The secondconcentration measuring part 264 may include a reactor 265, a reagentsupply part or reagent supplier 266, a correction chemical solutionsupply part or correction chemical solution supplier 267, and ameasurement electrode 268. The reactor 265 may have a bath shape. Thereactor 265 may have a space for receiving a chemical solution, areagent, and a correction chemical solution. The reagent supply part 266may include a reagent supply source 266 a, a reagent supply line 266 b,and a reagent supply valve 266 c. The reagent supply line 266 b mayconnect the reagent supply source 266 a to the reactor 265 and maysupply the reagent into the reactor 265. The reagent supply valve 266 cmay be installed on the reagent supply line 266 b to control a supply ofthe reagent. The reagent may react with the chemical solution. Thereagent may dissolve silicon included or dispersed in the chemicalsolution. For example, the reagent may contain fluorine ions. Thereagent may include an acid solution. A ratio of the reagent to thechemical solution may range from about 0.5:1 to about 1.5:1. The reagentmay be maintained at a setting or predetermined temperature. The settingtemperature may be a temperature capable of dissolving the silicon ofthe chemical solution. For example, the setting temperature may be about35° C. to about 43° C. The measurement electrode 268 may measure thesilicon concentration of the chemical solution reacted with the reagent.The measurement electrode 268 may be an ion selective electrode. The ionselective electrode may be an electrode of which a potential is variedaccording to a concentration of specific ions. For example, when thesilicon included in the chemical solution is dissolved to react with thefluorine ions of the reagent, a potential according to the amount of thefluorine ions remaining in the reactor 265 may be measured through themeasurement electrode 268. The concentration of the silicon may beback-tracked or determined using the amount of the fluorine ions reactedwith the chemical solution. For example, the measurement electrode 268may include lanthanum (La). The measurement electrode 268 may compare apotential of a reference electrode and the potential of the measurementelectrode 268 after the measurement to measure a potential differencetherebetween. In an implementation, the second concentration measuringpart 264 may further include a heater. In certain embodiments, thereagent may extract the (e.g., excess) silicon included in the chemicalsolution.

The correction chemical solution supply part 267 may include acorrection chemical solution supply source 267 a, a correction chemicalsolution supply line 267 b, and a correction chemical solution supplyvalve 267 c. The correction chemical solution supply line 267 b mayconnect the correction chemical solution supply source 267 a to thereactor 265 and may provide the correction chemical solution into thereactor 265. The correction chemical solution supply valve 267 c may beinstalled on the correction chemical solution supply line 267 b tocontrol a supply of the correction chemical solution. The correctionchemical solution may be the same as the chemical solution. Thecorrection chemical solution may have the same concentrations as ordifferent concentrations from the chemical solution. The correctionchemical solution may include silicon of a predetermined concentration.

Referring to FIGS. 1 and 3, a waste solution of which the concentrationmeasurement is or has been completed in the concentration measurementpart 260 may be exhausted into the waste solution treating part 280. Thewaste solution may include at least one of the chemical solution, thereagent, or the correction chemical solution. The waste solutiontreating part 280 may include a collection line 270, a first collectiontank 282, a second collection tank 285, a third collection line 289, andan exhaust line 290. The waste solution treating part 280 may exhaustthe waste solution in such a way to help prevent silicon from beingextracted, precipitated, or separated from the chemical solutionincluding high-concentration silicon.

The collection line 270 may connect the concentration measuring part 260to the waste solution treating part 280. The collection line 270 mayconnect the concentration measuring part 260 to the first and secondcollection tanks 282 and 285 to supply the waste solution that has beencompletely measured in the concentration measuring part 260 into thefirst and second collection tanks 282 and 285. The collection line 270may include a first collection line 270 a and a second collection line270 b. The first collection line 270 a may connect the firstconcentration measuring part 262 to the first collection tank 282, andthe second collection line 270 b may connect the second concentrationmeasuring part 264 to the second collection tank 285. As illustrated inFIG. 3, in an implementation, the first and second collection lines 270a and 270 b may share a portion. In an implementation, the first andsecond collection lines 270 a and 270 b may be provided independently ofeach other.

The first collection tank 282 may collect the waste solution measured inthe first concentration measuring part 262. At this time, the wastesolution collected in the first collection tank 282 may include thechemical solution. The second collection tank 285 may collect the wastesolution measured in the second concentration measuring part 264. Atthis time, the waste solution collected in the second collection tank285 may include at least one of the chemical solution, the reagent, orthe correction chemical solution. For example, the waste solutionexhausted from the second concentration measuring part 264 may be amixed solution of the chemical solution and the reagent. The secondcollection tank 285 may include a temperature sensor 287 and a heater288. The temperature sensor 287 and the heater 288 may adjust atemperature of the second collection tank 285 such that the temperatureof the second collection tank 285 meets a setting or predeterminedtemperature. The setting temperature may be a temperature at which thereagent included in the waste solution dissolves silicon included in thechemical solution and/or the correction chemical solution. For example,the setting temperature may range from about 35° C. to about 43° C. Thethird collection line 289 may connect the first collection tank 282 tothe second collection tank 285. When an additional dissolution operationis completed in the second collection line 285, a collection valve 289 ainstalled on the third collection line 289 may be opened to supply thewaste solution from the second collection tank 285 into the firstcollection tank 282. The additional dissolution operation may helpensure that silicon included in the waste solution received in thesecond collection tank 285 is additionally dissolved. The exhaust line290 may extend from the first collection tank 282. The exhaust line 290may exhaust the waste solutions mixed with each other in the firstcollection tank 282 to the outside. In an implementation, the exhaustline 290 may be connected to a main exhaust line in the substratetreating apparatus 1. In an implementation, the exhaust line 290 may beconnected directly to the main exhaust line.

FIG. 4 illustrates a flow chart of a method of treating a substrateaccording to some embodiments. FIG. 5A illustrates a flow chart of aprocess of measuring a water concentration and a silicon concentrationof FIG. 4. FIG. 5B illustrates a flow chart of a process of exhausting awaste solution of FIG. 4. FIG. 5C illustrates a flow chart of a processof processing data of FIG. 4. FIGS. 6A to 6E illustrate views of stagesin the method of treating a substrate of FIG. 4. FIGS. 7A and 7Billustrate graphs according to a process of processing data.Hereinafter, a method of treating a substrate will be described withreference to FIGS. 4, 5A to 5C, 6A to 6E, 7A, and 7B. Arrows show a flowof a fluid in FIGS. 6A to 6E. In FIGS. 6A to 6E, closed valves are shownby valves of which the insides are filled with black color, and openedvalves are shown by valves of which the insides are empty.

Referring to FIGS. 4, 5A, and 6A, the chemical solution may be suppliedinto the concentration measuring part 260 through the sampling line 240(S10). The first sampling valve 242 a of the first sampling line 240 aand the second sampling valve 242 b of the second sampling line 240 bmay be opened to supply the chemical solution into the firstconcentration measuring part 262 and the second concentration measuringpart 264, respectively.

Referring to FIGS. 4, 5A, and 6B, a water concentration and a siliconconcentration of the chemical solution may be measured (S20). The firstconcentration measuring part 262 may measure the water concentration ofthe chemical solution (S212). The first concentration measuring part 262may correspond to a water concentration measuring part illustrated inFIGS. 5A and 5B. The first concentration measuring part 262 may includethe optical measuring part. For example, the first concentrationmeasuring part 262 may include the optical measuring part using thenear-infrared rays. For example, the first concentration measuring part262 may irradiate the near-infrared rays to the chemical solution andmay measure the absorption degree (i.e., the absorbance) from awavelength band of a near-infrared ray, absorbed by water, amongnear-infrared rays reflected from the chemical solution. The firstconcentration measuring part 262 may convert the measured absorbanceinto a water content to measure the water concentration. The firstconcentration measuring part 262 may convert the measured waterconcentration into a concentration of phosphoric acid included in thechemical solution.

The second concentration measuring part 264 may supply the reagent intothe chemical solution received in the reactor 265 to measure the siliconconcentration of the chemical solution (S222 and S224). The secondconcentration measuring part 264 may correspond to a siliconconcentration measuring part illustrated in FIGS. 5A and 5B. The reagentmay react with the chemical solution. The reagent may dissolve siliconincluded or dispersed in the chemical solution. For example, the reagentmay contain fluorine ions. The reagent may include the acid solution.The ratio of the reagent to the chemical solution may range from about0.5:1 to about 1.5:1. The reagent may be maintained at the settingtemperature. The setting temperature may be a temperature capable ofdissolving the silicon of the chemical solution. For example, thesetting temperature may range from about 35° C. to about 43° C. Themeasurement electrode 268 may measure the silicon concentration of thechemical solution reacted with the reagent. In some embodiments, themeasurement electrode 268 may measure the concentration of the fluorineions, thus the concentration of the silicon may be back-tracked ordetermined based on the amount of the fluorine ions reacted with thechemical solution (e.g., based on the total amount of fluorine ionsprovided to the reactor and the amount of fluorine atoms remaining inthe reactor after reacting with the chemical solution). In someembodiments, the measurement electrode 268 may be the electrode of whichthe potential is varied according to a concentration of silicon ions.

Referring to FIGS. 4, 5B, and 6C to 6E, the waste solution completelymeasured in the concentration measuring part 260 may be exhausted (S40and S410). The waste solution may include at least one of the chemicalsolution, the reagent, or the correction chemical solution. The wastesolution measured in the first concentration measuring part 262 may besupplied into the first collection tank 282 through the first collectionline 270 a (S420). At this time, the waste solution supplied in thefirst collection tank 282 may include the chemical solution. The wastesolution measured in the second concentration measuring part 262 may besupplied into the second collection tank 285 through the secondcollection line 270 b (S430). At this time, the waste solution suppliedin the second collection tank 285 may include at least one of thechemical solution, the reagent, or the correction chemical solution. Forexample, the waste solution exhausted from the second concentrationmeasuring part 264 may be the mixed solution of the chemical solutionand the reagent. A temperature of the second collection tank 285 may becontrolled such that a temperature of the received waste solution meetsa setting or predetermined temperature (S432). The setting temperaturemay be a temperature at which the reagent included in the waste solutiondissolves silicon included in the chemical solution. For example, thesetting temperature may range from about 35° C. to about 43° C. When thetemperature of the second collection tank 285 meets the settingtemperature, the waste solution of the second collection tank 285 may besupplied into the first collection tank 282 (S434 and S436). Thereafter,the waste solutions mixed with each other in the first collection tank282 may be exhausted to the outside through the exhaust line 290 (S440).By these two exhausting processes, it is possible to help reduce and/orprevent a silicon deposit from being generated in the exhaust line 290and/or to prevent the exhaust line 290 from being clogged with thesilicon deposit.

Referring to FIGS. 4, 5C, 7A, and 7B, the control unit 30 may processdata using the measured water concentration and silicon concentration(S510). A mass or amount of the phosphoric acid included in the chemicalsolution may be constant, but a mass or amount of the silicon includedin the chemical solution may increase as the substrate treating processprogresses (e.g., as silicon is removed from the substrate). Inaddition, the substrate treating process may be performed at a hightemperature, and an amount of the water included in the chemicalsolution may vary greatly due to evaporation and inflow of water. Thus,the control unit 30 may calculate a variation in concentration of waterand a variation in concentration of silicon using the measured waterconcentration and silicon concentration of the chemical solution and maycalculate the dissolution amount of the silicon included in the chemicalsolution (S520 and S530). The water of the chemical solution may bedeionized water. Referred to FIG. 7A, the following equation 1 may beobtained by the measured and calculated data. As shown in the followingequation 1, the concentration variation d(C_(DIW)/dt of the water may beproportional to the concentration variation d(C_(Si))/dt of the silicon.In addition, the dissolution amount m_(Si) of the silicon of thechemical solution may be back-tracked or determined using a gradient aof the concentration variations and the mass m_(HP) of the phosphoricacid included in the chemical solution (see the following equation 2).At this time, the mass m_(HP) of the phosphoric acid may be apredetermined value.

$\begin{matrix}{\frac{d\left( C_{DIW} \right)}{dt} = {a\frac{d\left( C_{Si} \right)}{dt}}} & \left\lbrack {{Equation}\mspace{14mu} 1} \right\rbrack \\{a = {{- \frac{m_{HP}}{m_{Si}}} - 1}} & \left\lbrack {{Equation}\mspace{14mu} 2} \right\rbrack\end{matrix}$

A revised concentration C_(Si)(rev) of the silicon may be defined usingthe Equations 1 and 2, as illustrated in the following equation 3(S540). The revised concentration C_(Si)(rev) of the silicon may referto a concentration excluding water interference caused according to theconcentration variation of the water. The revised concentrationC_(Si)(rev) of the silicon may be defined using the measured siliconconcentration C_(Si) and a difference between the measured waterconcentration C_(DIW) and a reference water concentration C_(DIW)(ref).The reference water concentration C_(DIW)(ref) may be set at apredetermined time. For example, the control unit 30 may set asoft-sensor with respect to the revised silicon concentration.

$\begin{matrix}{{C_{Si}({rev})} = {C_{Si} - {\frac{1}{a}\left( {C_{DIW} - {C_{DIW}({ref})}} \right)}}} & \left\lbrack {{Equation}\mspace{14mu} 3} \right\rbrack\end{matrix}$

Thus, as illustrated in FIG. 7B, the control unit 30 may display themeasured silicon concentration {circle around (1)}, the measured waterconcentration {circle around (2)}, and the revised silicon concentration{circle around (3)}. The control unit 30 may set an interlock signalbased on the measured silicon concentration {circle around (1)}, themeasured water concentration {circle around (2)}, and the revisedsilicon concentration {circle around (3)}. For example, the control unit30 may set a first setting range of the measured silicon concentration{circle around (1)} and may generate a first interlock signal when themeasured silicon concentration {circle around (1)} is beyond or outsideof the first setting range. In addition, the control unit 30 may set asecond setting range of the revised silicon concentration {circle around(3)} and may generate a second interlock signal when the revised siliconconcentration {circle around (3)} is beyond or outside of the secondsetting range. The control unit 30 may set the first and secondinterlock signals in such a way that the first and second interlocksignals overlap with each other. In an implementation, the control unit30 may generate the interlock signal based on the measured waterconcentration {circle around (2)} or a temperature in the substratetreating apparatus 1. As a result, it is possible to easily monitorand/or control the substrate treating apparatus 1 using the chemicalsolution, and the reliability of the substrate treating apparatus 1 maybe improved.

FIG. 8 illustrates a flow chart of a method of treating a substrateaccording to some embodiments. FIG. 9A illustrates a flow chart of aprocess of cleaning a silicon concentration measuring part of FIG. 8.FIG. 9B illustrates a graph of a trend of a measured siliconconcentration. Hereinafter, a method of treating a substrate will bedescribed with reference to FIGS. 8, 9A and 9B. Steps S10, S20, S40, andS50 of the substrate treating method of FIG. 8, except a step S30 ofcleaning the silicon concentration measuring part, may be the same as orsimilar to the steps S10, S20, S40, and S50 described with reference toFIGS. 4, 5A to 5C, 6A to 6E, 7A, and 7B. Thus, in the presentembodiment, the same descriptions as in the embodiments of FIGS. 4, 5Ato 5C, 6A to 6E, 7A, and 7B may be omitted or mentioned briefly for thepurpose of ease and convenience in explanation.

Referring to FIGS. 8 and 9A, the second concentration measuring part 264(i.e., the silicon concentration measuring part 264) may be cleaned inresponse to a control signal of the control unit 30 before, during, orafter the measurement of the silicon concentration (S30). The controlunit 30 may control the silicon concentration measuring part 264 in sucha way that a mode of the silicon concentration measuring part 264 isswitched between a measurement mode and a cleaning mode. In themeasurement mode, the silicon concentration measuring part 264 maymeasure the silicon concentration. In the cleaning mode, the inside ofthe silicon concentration measuring part 264 may be cleaned. In someembodiments, the control unit 30 may control the silicon concentrationmeasuring part 264 such that the silicon concentration measuring part264 may be periodically or non-periodically cleaned. The control unit 30may set the cleaning mode of the silicon concentration measuring part264 to one of a periodic progress mode and a non-periodic progress mode(S310).

When the cleaning mode is set to the periodic progress mode, the controlunit 30 may set a setting period and may determine whether cleaning ofthe silicon concentration measuring part 264 is performed according towhether the setting period passes (S320 and S322). When the settingperiod passes, the control unit 30 may control the concentrationmeasuring part 260 such that a reagent may be provided into the reactor265 until the reagent in the reactor 265 reaches a setting level (S324).The reagent may dissolve silicon remaining in the reactor 265. Inaddition, the reagent may dissolve silicon particles formed on themeasurement electrode 268. For example, the reagent may contain fluorineions. The reagent may include an acid solution. The reagent may beheated to a setting temperature (S326). For example, the settingtemperature may range about 35° C. to about 43° C. A stirring processmay be performed to smoothly perform the reaction between the reagentand the silicon (S328). When a setting time passes, the control unit 30may control the substrate treating apparatus 1 to exhaust the reagentthrough the second collection tank 285 (S330 and S332). The setting timemay range from about 15 minutes to about 30 minutes.

When the cleaning mode is set to the non-periodic progress mode, thecontrol unit 30 may control the concentration measuring part 260 suchthat a correction chemical solution may be provided into the reactor 265(S340). The correction chemical solution may be the same as the chemicalsolution. Concentrations of the correction chemical solution may beequal to or different from those of the chemical solution. Thecorrection chemical solution may contain silicon having a predeterminedconcentration (i.e., the reference concentration). The control unit 30may control the concentration measuring part 260 to measure a siliconconcentration of the correction chemical solution supplied in thereactor 265 (S342 and S344). When the measured silicon concentration ofthe correction chemical solution is beyond or outside of a predeterminedreference concentration range, cleaning of the silicon concentrationmeasuring part 264 is required. Thus, when the measured siliconconcentration of the correction chemical solution is beyond or outsideof the reference concentration range, the control unit 30 may controlthe concentration measuring part 260 to supply the reagent into thecorrection chemical solution of the reactor 265 (S346 and S324).Thereafter, the cleaning process using the reagent may be performed asdescribed in the steps 5328, S330, and S332. When the measured siliconconcentration of the correction chemical solution is beyond or outsideof the reference concentration range and satisfies an auto-correctionsetting condition, auto-correction may be performed (S346, S348, andS350). The auto-correction may include zero-point correction. After theauto-correction is completed, a silicon concentration of the correctionchemical solution may be re-measured (S352). When the re-measuredsilicon concentration is beyond the reference concentration range, thecontrol unit 30 may continuously perform the cleaning process. On thecontrary, when the re-measured silicon concentration is in the referenceconcentration range, the control unit 30 may complete the cleaningprocess and may switch the silicon concentration measuring part 260 tothe measurement mode (S360).

Referring to FIG. 9B, a trend of the concentration measured by thesilicon concentration measuring part 264 may be graphed. In FIG. 9B, aline A and a line B indicate time points at the cleaning process of thesilicon concentration measuring part 264 is performed. At this time, itis recognized that differences between measured silicon concentrationvalues may occur as a measuring time of the silicon concentrationmeasuring part 264 (i.e., a circulating time of the chemical solution)increases. For example, a peak P of the measured silicon concentrationvalues may occur at a specific time point. In addition, the measuredsilicon concentration value may be corrected immediately after thecleaning process is performed on the silicon concentration measuringpart 264. Thus, it is recognized that the cleaning process of thesilicon concentration measuring part 264 may be needed. Furthermore, acleaning period of the silicon concentration measuring part 264 may beset using this trend by the control unit 30.

The cleaning process of the silicon concentration measuring part 264 maybe performed, and silicon accumulated in the reactor 265 may be removed.In addition, silicon particles formed on the surface of the measurementelectrode 268 may also be removed. Thus, it is possible to help preventa measurement error of the measured silicon concentration, and thereliability of the substrate treating apparatus 1 may be improved.

By way of summation and review, in an etching process, it may bedesirable to maintain a high etch selectivity between an etch targetlayer and another layer and to minimize defects caused by reactionby-products generated during the etching process. Thus, an etchingcomposition may be capable of improving an etch selectivity betweendifferent layers and of reducing occurrence of unnecessary reactionby-products. For example, when the etching process is performed using achemical solution including a phosphoric acid aqueous solution and ahigh-concentration silicon compound, a layer disposed on a substrate maybe etched to increase a silicon content in the chemical solution as theetching process progresses. In this case, abnormal growth could occur onthe substrate and/or trouble or malfunction of equipment may be causedby a silicon deposit occurring in the equipment.

In the embodiments described above, the chemical solution for performingthe etching process on a substrate is described as an example. In animplementation, the embodiments may be applied to various processes oftreating a substrate using a mixed chemical solution. In addition, inthe above embodiments, the chemical solution including the phosphoricacid aqueous solution and the silicon compound is described as anexample. In an implementation, the chemical solution may include otherconstituents. Moreover, the process of treating a substrate using thechemical solution including the silicon compound of a high content at ahigh temperature is described as an example in the above embodiments. Inan implementation, the embodiments may be applied to various chemicalsolution supply units supplying a chemical solution under the samecondition.

According to some embodiments, the silicon concentration and the waterconcentration of the chemical solution may be measured, and suchmeasurement data may be used to control the silicon concentration. Insome embodiments, the revised silicon concentration, which excludes theinterference of the water, may be obtained based on the variation in themeasured water concentration and the variation in the measured siliconconcentration. Thus, it is possible to accurately control the siliconconcentration of the chemical solution and to help reduce and/or preventthe abnormal growth that may occur on a substrate by thehigh-concentration silicon. In addition, the silicon concentration maybe increased during the process by the chemical solution which includesthe high-concentration silicon and may be controlled or maintained at ahigh temperature, the silicon concentration of the chemical solution maybe controlled by cleaning the silicon concentration measuring partand/or by the agent reaction of the exhaust operation. As a result, itis possible to reduce and/or prevent trouble or malfunction of theapparatus from occurring by a silicon deposit formed in the apparatus.In addition, the measurement error of the silicon concentration may bereduced and/or prevented.

The embodiments may provide an apparatus and method of treating asubstrate using a chemical solution including a phosphoric acid aqueoussolution and a silicon compound.

The embodiments may provide an apparatus and method of treating asubstrate, which are capable of measuring both a silicon concentrationand a water concentration.

The embodiments may provide an apparatus and method of treating asubstrate, which are capable of preventing system trouble or systemmalfunction caused by a silicon deposit when a chemical solutionincluding a high-temperature and high-concentration silicon compound isused.

Example embodiments have been disclosed herein, and although specificterms are employed, they are used and are to be interpreted in a genericand descriptive sense only and not for purpose of limitation. In someinstances, as would be apparent to one of ordinary skill in the art asof the filing of the present application, features, characteristics,and/or elements described in connection with a particular embodiment maybe used singly or in combination with features, characteristics, and/orelements described in connection with other embodiments unless otherwisespecifically indicated. Accordingly, it will be understood by those ofskill in the art that various changes in form and details may be madewithout departing from the spirit and scope of the present invention asset forth in the following claims.

What is claimed is:
 1. A substrate treating apparatus, comprising: asubstrate treater that treats a substrate in a bath using a chemicalsolution, the chemical solution including a phosphoric acid aqueoussolution and a silicon compound; a chemical solution supplier thatsupplies the chemical solution having a first temperature to thesubstrate treater; and a controller that controls the substrate treaterand the chemical solution supplier, wherein the chemical solutionsupplier includes: a chemical solution circulator that circulates thechemical solution in the bath, a sampling line that is branched thechemical solution circulator to extract a sample of the chemicalsolution, a concentration measurer that is connected the sampling lineand measures concentrations of the sample of chemical solutions having asecond temperature lower than the first temperature, and a wastesolution treater that drains a waste solution of which concentrationmeasurement has been completed in the concentration measurer, whereinthe concentration measurer includes: a first concentration measurer thatis connected between the sampling line and the waste solution treater,and measures a water concentration of the chemical solution; and asecond concentration measurer that is connected in parallel with thefirst concentration measure between the sampling line and the wastesolution treater, and measures a silicon concentration of the chemicalsolution, wherein the controller controls the on-off valve to supply asample of the chemical solution having a second temperature that islower than the first temperature to the first concentration measurer andthe second concentration measurer, and wherein the controller calculatesa revised silicon concentration of the chemical solution in the bath atthe first temperature based on the water concentration and the siliconconcentration of the sample of the chemical solution at the secondtemperature.
 2. The substrate treating apparatus as claimed in claim 1,wherein the sampling line includes an on-off valve, and wherein thecontroller controls the on-off valve to supply the chemical solution tothe first concentration measurer and the second concentration measurer.3. The substrate treating apparatus as claimed in claim 2, wherein thesecond concentration measurer includes a measurement electrode that isan ion selective electrode.
 4. The substrate treating apparatus asclaimed in claim 3, wherein the second concentration measurer furtherincludes: a reactor that receives the chemical solution; and a reagentsupplier that supplies a reagent into the reactor, the reagent beingreactable with the chemical solution, and wherein the measurementelectrode measures the silicon concentration in the reactor.
 5. Thesubstrate treating apparatus as claimed in claim 4, wherein thecontroller controls the second concentration measurer to periodically ornon-periodically clean the reactor.
 6. The substrate treating apparatusas claimed in claim 5, wherein the controller controls the secondconcentration measurer such that the reagent is supplied into thereactor to remove silicon remaining in the reactor when the reactor iscleaned.
 7. The substrate treating apparatus as claimed in claim 5,wherein the second concentration measurer further includes a correctionchemical solution supplier that supplies a correction chemical solutioninto the reactor, the correction chemical solution correcting ameasurement error of the silicon concentration.
 8. The substratetreating apparatus as claimed in claim 7, wherein: the controllercontrols the second concentration measurer such that the correctionchemical solution having a reference concentration is supplied into thereactor and such that the silicon concentration is then measured, whenthe reactor is non-periodically cleaned, and the controller determineswhether cleaning of the reactor is performed according to whether themeasured silicon concentration is beyond a reference concentration rangeof the reference concentration.
 9. The substrate treating apparatus asclaimed in claim 4, wherein the waste solution treater includes: a firstcollection tank in which the chemical solution that was measured in thefirst concentration measurer is collected; and a second collection tankin which the reagent and the chemical solution that was measured in thesecond concentration measurer is collected.
 10. The substrate treatingapparatus as claimed in claim 9, wherein: the second collection tankincludes a heater, the controller controls the heater to heat thechemical solution and the reagent collected in the second collectiontank to a setting temperature, and when the chemical solution and thereagent reach the setting temperature, the controller controls the wastesolution treater such that the chemical solution and the reagent in thesecond collection tank is supplied into the first collection tank. 11.The substrate treating apparatus as claimed in claim 2, wherein thecontroller calculates the revised silicon concentration, excludinginterference of water included in the chemical solution, based on avariation in the water concentration measured by the concentrationmeasurer and a variation in the silicon concentration measured by theconcentration measurer.
 12. The substrate treating apparatus as claimedin claim 11, wherein the controller generates an interlock signal whenthe revised silicon concentration is beyond a predetermined settingrange.
 13. The substrate treating apparatus as claimed in claim 11,wherein: the controller sets a first setting range of the siliconconcentration measured by the second concentration measurer and a secondsetting range of the revised silicon concentration, and the controllergenerates an interlock signal when the revised silicon concentration isbeyond the first setting range or when the measured siliconconcentration is beyond the second setting range.
 14. The substratetreating apparatus as claimed in claim 2, wherein the firstconcentration measurer includes an optical measurer that uses anear-infrared ray.